CN101108903A - Nitrile rubber sizing material using black pigment modifier - Google Patents
Nitrile rubber sizing material using black pigment modifier Download PDFInfo
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- CN101108903A CN101108903A CNA2006100366441A CN200610036644A CN101108903A CN 101108903 A CN101108903 A CN 101108903A CN A2006100366441 A CNA2006100366441 A CN A2006100366441A CN 200610036644 A CN200610036644 A CN 200610036644A CN 101108903 A CN101108903 A CN 101108903A
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Abstract
The invention discloses a NBR compounds using the carbon black modifier, which is mixed by the following materials based on the mass portion: NBR dosage is 100 of the mass portion; zinc oxide dosage is 0.1 to 20 of the mass portion; stearic acid dosage is 0.1 to 20 of the mass portion; aging inhibitor dosage is 0.1 to 20 of the mass portion; accelerant dosage is 0.1 to 20 of the mass portion; sulphur dosage is 0.1 to 20 of the mass portion; carbon black dosage is 0.1 to 150 of the mass portion; plasticizer dosage is 0.1 to 150 of the mass portion and carbon black modifier dosage is 0.1 to 7.0 of the mass portion. The adoption of the carbon black modifier overcomes the defects existing in the carbon black modifier and the dispersant frequently used in the current rubber industry. Compared with the carbon black modifier and the dispersant frequently used in the current rubber industry, the carbon black modifier mentioned above has no effect on the curing speed of the sizing and obviously increases the processability of the NBR compounds of the carbon black with high filling and reinforcing abilities and the physical and mechanical properties, heat-resistant quality, oil resistance and compression set resistance of the vulcanizate.
Description
Technical field
The present invention relates to a kind of nitrile rubber sizing material that uses black pigment modifier.
Background technology
Paracril NBR is a kind of specialty elastomer that adopts letex polymerization to form by vinyl cyanide and divinylic monomer.Have polar itrile group group on the NBR molecular chain, give the anti-nonpolar wet goods excellent properties of its excellence, be mainly used in and make the oil resisting rubber goods, be widely used in fields such as automotive industry, aerospace, oilfield chemical, light and textile industries, electric wire and material of construction.
Under long term thermal air or deep fat aging condition, the NBR goods are easily because the existence of unsaturated double-bond in the molecular structure of NBR, and chemical stability is low under hot conditions, with contacting of oxygen, ozone, other medium, the aging of NBR be can promote, sclerosis and embrittlement phenomenon produced.Therefore, compare with other oil resisting rubber kind such as acrylic elastomer (ACM), chlorosulfonated polyethylene (CSM), epichlorohydrin rubber (CO/ECO), hydrogenated nitrile-butadiene rubber (HNBR), viton (FPM), fluosilicic rubber (FSPM) etc., the thermotolerance of NBR is relatively poor, and long-time use temperature scope is at-45～120 ℃.The market value of NBR is minimum in above-mentioned oil resisting rubber kind, and processing characteristics is best but by contrast.
Along with oil and developing of automobile industry, fuel oil and the lubricating oil of keeping automotive power work constantly develop to the high performance direction, operating temperature range is handed over wide, various additives in the working medium oil strengthens the erosion action of rubber, the pressure that bears during work increases, and the performance of oil resisting rubber has been proposed harsh more requirement.For example, require the NBR cross-linked rubber to have higher intensity, and lower compression set is at high temperature arranged.Therefore, improve the over-all properties of the tangible NBR of superiority of effectiveness, part replaces other oil resisting rubber kind of high price significant.
Without the NBR cross-linked rubber of reinforcement, physical and mechanical properties is very low, has only 1.5～3MPa as tensile strength, must add the performance that strengthening agent improves cross-linked rubber and just can make NBR have practical value.
The effect of filler Reinforced Rubber, except the character and the interaction between structures shape rubber and the filler of filler itself, the dispersion effect of filler in rubber also is an important factor.Interactional balance between dispersion state decision rubber-filler interaction of filler and the filler.Being uniformly dispersed of filler be with packing material size, surperficial intrinsic activity or modification after the active the same significant effects factor of gained.
Carbon black is the most important strengthening agent of rubber industry, has become the rubber ingredients of consumption maximum.The carbon black Reinforced Rubber, carbon black aggregate plays a part cross-link bond, the common filler-rubber network of forming between carbon black and the rubber; Rubber molecular chain can be at the carbon black particle surface sliding, and with respect to pure glue network, rubber molecule chain-unfolding and orientation are more obvious, can bear bigger stress, and sooty particle diameter, structural, surfactivity play an important role in reinforcing effect.
Usually, the sooty particle diameter is more little, and specific surface area is big more, and is structural high more, and then the reinforcing property to rubber is good more.Performances such as the hardness of cross-linked rubber, tensile strength, stress at definite elongation rise with the minimizing of particle size carbon black in certain amount ranges, but the shock elasticity of cross-linked rubber diminishes, it is big that compression set becomes, dynamic heat build up raises, heat-resisting and winter hardiness variation, and sizing material is given birth to heat increase, dispersity of carbon black variation, processing difficulties when mixing.
Unfortunately, give birth to Synergist S-421 95s such as heat is big, quick heating, powder when the processing characteristics characteristics of NBR are mixing and be difficult for sneaking into, under high temperature and shearing force effect, easily produce the structurizing effect.Along with the rising of melting temperature and the prolongation of process period, viscosity can constantly increase, especially when filling high structure, big, the highly active carbon black of specific surface area such as high wear-resistant carbon black (HAF) and intermediate super abrasion furnace black (ISAF) in a large number, the viscosity of sizing material can sharply increase because of the generation of gel, make mixing processing more difficult, mobile variation; Simultaneously, the thermotolerance and the winter hardiness of cross-linked rubber are reported to the leadship after accomplishing a task, and it is big that compression set becomes.
Seek out the NBR cross-linked rubber of the high combination property of high strength, low compression set, thermotolerance, cold tolerance excellence, the high reinforcement carbon black that must add high consumption strengthens, must solve sooty modification, the mixing problems such as heat is big, dispersion of giving birth to simultaneously, the contradiction of reply goods multinomial performance mutual restriction is to reach the overall equilbrium of every performance index.
Sooty modification and be dispersed with the people and studies have shown that, tetra-sulfurized pair (triethoxy propyl group) silane (Si69) is a kind of multi-functional silane coupling agent, can be used as vulcanizing agent, promoting agent and the sooty properties-correcting agent and the dispersion agent of rubber, can reduce the viscosity of sizing material, improve tensile strength, wear resistance, fatigue resistance and the elasticity of cross-linked rubber.Compare with unmodified carbon black through Si69, binary aliphatic or trivalent alcohol surface modified carbon black, the hysteretic properties of the natural rubber of giving (NR)/cis-1,4-polybutadiene rubber (BR)/NBR tertiary blending cross-linked rubber and low temperature resistant, high temperature and wear resistance improve.In addition, warp is to the cross-linked rubber of the carbon black filled NR of modifications such as aromatic polyhydroxy compounds such as Resorcinol, Phloroglucinol, pyrocatechol or pyrogaelol, and static mechanical performance and dynamic properties all have improvement.
Research is in the past also found, fills NR with the Si69 modified carbon black, and the oxy radical of carbon blacksurface forms certain chemistry with Si69 and is connected, and makes and has generated " flexible cross-link bond " between NR molecular chain and the carbon black.Compare with " rigid " Chemical bond key of carbon black and NR, so flexible cross-link bond has increased that the interface combines between NR and the carbon black, be more conducive to the NR molecular chain in the carbon blacksurface slippage, make the suffered stress of NR molecule more even, thereby improved elasticity, wear resistance, the tensile strength of carbon black filled cross-linked rubber; Simultaneously, part Si 69 also may enter in the active site of carbon blacksurface space by physical diffusion, forms physical adsorption, and carbon black after the modification is easier to be disperseed in NR thereby make, and has improved NR and sooty interfacial interaction.Along with the increase of Si69 consumption, the dispersion of carbon black in NR is tending towards even.When Si69 consumption between sooty 3～6% or when bigger, the particle diameter of carbon black coacervate is littler, interface between carbon black enrichment region and the NR molecular chain enrichment region is fuzzyyer, carbon black forms netted continuous structure mutually in a wider context, the coupled action of Si69 shows owing to can combine between carbon black and the NR molecular chain better.
But, in rubber mixing process, Si69 need just can make it fully to react with carbon black in higher temperature (under as 120～140 ℃) the mixing long period, especially be not suitable for being used for giving birth to when mixing heat big, when high-temperature mixing, easily produce gel, fill high reinforcement sooty NBR sizing material; In addition, because the singularity of Si69 molecular structure, fracture will take place and cause the crosslinking reaction of rubber molecular chain when melting temperature is higher in its polysulfidic bond, cause the incipient scorch of sizing material easily; Also have, higher price has also limited the application of Si69.
Processing aid is that rubber physical mechanical property is had no adverse effects, can improve greatly comprise mixing, roll, extrude, processing characteristics such as moulding, also might improve the dispersion of filler and shorten the material of mixing time.From main effect classification, processing aid comprises lubricant, dispersion agent, leveler, tackifier and releasing agent.Wherein, some lubricant and dispersion agent improve carbon black or the dispersion of white carbon black in rubber.
The main effect of lubricant is a flowability of improving sizing material, between the sizing material, play lubricated, buffer action between the metallic surface of sizing material and processing units.Simultaneously, also might improve the flowability of sizing material by the dispersion that improves filler.Common lubricant has metallic soap class, hydro carbons of higher fatty acid, fatty acid ester and lipid acid thereof etc.Common mixture, paraffin and the Vaseline etc. that stearic acid, Zinic stearas, fatty acid ester or itself and insoluble filler are arranged.But except that Zinic stearas, the thermotolerance instability of these lubricants can delay the sulfuration of sizing material and the physical and mechanical properties of reduction cross-linked rubber when consumption is big.
How to make Nano fillings such as carbon black, white carbon black bring into play due effect in rubber, its dispersion in rubber becomes key factor.
When general polydiene cooperates, can make Nano filling under dynamic condition, can not form bigger aggregate by adding coupling agents such as Si69, perhaps add suitable dispersion agent, make rubber/Nano filling reach nano level and disperse.
The main effect of rubber dispersion agent is to improve the dispersivenesses of filler in rubber such as carbon black, white carbon black, shortens mixing time.Some flow ability modifying agent also helps dispersion, the shortening mixing time of filler and reduces the effect of compound viscosity.
Table 1 is present rubber industry fillers dispersed agent and a flow ability modifying agent commonly used.Though the kind of dispersion agent is many, main component is the mixture of fatty acid ester and metallic soap class and interfacial agent.Its mechanism of action mainly is the effect by tensio-active agent, and fatty acid and metallic soap class dispersion agent are attracted on the filler grain, cause the fragmentation of filler grain aggregate, thereby makes its dispersed raising.
These dispersion agents and flow ability modifying agent have some common characteristic, promptly are self to be not easy cohesion, and interfacial activity is bigger, and easy and some polarity or the adsorption of apolar substance generation certain physical are more stable under cold condition.In the time of in joining rubber, can moistening filler, filler grain produced intercept, centrifugation, thereby reduce interaction between filler grain, make it be not easy to assemble, thereby improve the dispersion of filler in rubber, reduce the viscosity of sizing material, improve its flowability.
The positive usual amounts of these dispersion agents and flow ability modifying agent is 2.0～5.0 mass parts.Under positive usual amounts, to the not significantly influence of performance of cross-linked rubber.Because the structure and the performance characteristics of dispersion agent and flow ability modifying agent, when consumption is excessive, meeting obviously weakens between rubber and the filler, the interaction between the rubber molecule, delays the sulfuration of sizing material and physical and mechanical properties such as tensile strength, hardness and the thermotolerance etc. of reduction cross-linked rubber.
Table 1: fillers dispersed agent and flow ability modifying agent that rubber is commonly used
| Trade(brand)name | Main component | Effect |
| The easy plain T-78 of glue | The metallic soap based mixtures of interfacial agent | Carbon black disperser |
| PEG (molecular weight 400～6000) | Polyoxyethylene glycol | The active dispersion agent of white carbon black |
| WB16 | The mixture of calcium soap and unsaturated fatty acid amide | Help the dispersion of filler, shorten mixing time, reduce compound viscosity |
| WB212 | The mixture of high-molecular weight fatty acid ester and active filler | |
| WB222 | The mixture of high-molecular weight lipid acid hydrocarbon and fatty acid ester | |
| W33 | Natural acid and its carboxylate and saponified mixture | |
| SL-272 | Organic soap mixture | The dispersion agent of white carbon black, the flow ability modifying agent of filling white carbon black sizing material |
| SL-173 | ||
| Mo Deli 935P | The metallic soap mixture of synthetic interfacial agent | Flow ability modifying agent |
| Aflux 12 | Fatty acid ester and the mixture that is mixed with the hydro carbons of inert filler | Dispersion agent |
| Aflux 16 | The mixture of natural fat acid calcium salt and acid amides adipocere | Flow ability modifying agent |
| Aflux 25 | The mixture of lipid acid and isoalkane wax | Flow ability modifying agent, lubricant |
| Aflux 42 | The mixture of Fatty Alcohol(C12-C14 and C12-C18) and fatty ester | The fillers dispersed agent |
| Aflux 42M | The anhydrous mixture of Fatty Alcohol(C12-C14 and C12-C18) and fatty acid ester | |
| Aktiplast T | Unsaturated lipid ester acid zinc soap | The sooty dispersion agent, the flow ability modifying agent of carbon black-filled sizing material |
| Aktiplast T60 | The mixture of unsaturated lipid ester acid zinc soap and mineral filler | |
| Aktiplast PP | The saturated fatty acid zinc soap | |
| Aktiplast GT | The saturated fatty acid zinc soap | The flow ability modifying agent of filling white carbon black sizing material |
| Aktiplast ST | The mixture of special zinc soap and dispersion agent | The dispersion agent of white carbon black |
| Dispergator FL | The mixture of synthetic resins and interfacial agent thereof and filler | Improve the dispersion of blended rubber and filler |
| Z-210 | Dissolve in the saturated and unsaturated zinc soap class of rubber |
During by a large amount of high rigidity NBR goods of filling of high structure, fine particle carbon black, because the mixing heat of giving birth to is big, cause the sizing material processing difficulties in preparation, rubber mobility is poor, easily shortcoming such as incipient scorch.At this moment can add the processing characteristics that fillers dispersed agent or flow ability modifying agent improve sizing material.But, different with non-polar rubbers such as NR, BR, because NBR is the bigger rubber clone of polarity, Intermolecular Forces, the adding of these dispersion agents or flow ability modifying agent, easier between the NBR molecule, play plasticising, lubricated, buffer action between NBR molecule and the carbon black, interaction between NBR and the filler, between the NBR molecule is littler, the easier slippage of NBR molecular chain under heat and stress, thus have a strong impact on the key propertys such as tensile strength, compression set, thermotolerance of NBR cross-linked rubber.
Summary of the invention
It is better that patent purpose of the present invention provides a kind of high rigidity, high strength, snappiness, thermotolerance and winter hardiness, the nitrile rubber sizing material that the sizing material processing characteristics is good; Fill the good carbon black of reinforcing property of high consumption, solve the sooty modification, sooty disperses and in the heat-proof aging process high reactivity carbon black continue to take place to interact and cause problem such as cross-linked rubber accelerate hardening with rubber molecular chain.
To the effect that described nitrile rubber sizing material of the present invention is mixed by mass fraction by following material: NBR dosage 100 mass parts; Zinc oxide dosage 0.1～20 mass parts; Stearic acid dosage 0.1～20 mass parts; Aging inhibitor dosage 0.1～20 mass parts; Accelerator level 0.1～20 mass parts; Sulphur dosage 0.1～20 mass parts; Carbon black loading 0.1～150 mass parts; Plasticizer consumption 0.1～150 mass parts; Black pigment modifier consumption 0.1～7.0 mass parts;
Further nitrile rubber sizing material is mixed by mass fraction by following material: NBR dosage 100 mass parts; Zinc oxide dosage 6.0 mass parts; Stearic acid dosage 1.2 mass parts; Anti-aging agent TMDQ consumption 1.5 mass parts; Antioxidant MB I consumption 1.5 mass parts; Promotor TB
zTD consumption 2.0 mass parts; Accelerator CBS consumption 1.5 mass parts; Sulphur dosage 0.5 mass parts; High wear-resistant carbon black consumption 50 mass parts; Plasticizer DOP consumption 5.0 mass parts; Black pigment modifier consumption 2.0～6.0 mass parts;
Above-mentioned black pigment modifier is the compound of functional groups such as fluorine-containing, ehter bond and unsaturated double-bond.
Above-mentioned anti-aging agent is that TMDQ is 2,2, and 4-trimethylammonium-1,2-dihydroxyl caye quinoline polymkeric substance and MBI are also using of 2-mercaptobenzimidazole.
Above-mentioned promotor is TB
zTD is that tetra-benzyl thiram disulfide and CBS are also using of N cyclohexyl 2 benzothiazole sulfenamide.
Above-mentioned softening agent is that DOP is a dioctyl phthalate (DOP).
Above-mentioned carbon black is a high wear-resistant carbon black.
Above-mentioned paracril (NBR) is the blend that contains vinyl cyanide rubber or contain vinyl cyanide rubber.
Above-mentioned anti-aging agent can be any anti-aging agent in the rubber industry, and consumption is 0.1～20 mass parts;
Above-mentioned promotor can be any promotor in the rubber industry, and consumption is 0.1～20 mass parts;
Above-mentioned softening agent can be any plasticizer in the rubber industry, and consumption is 0.1～150 mass parts.
Black pigment modifier of the present invention is the compound of functional groups such as fluorine-containing, the ether of a kind of specific molecular weight and distribution thereof and unsaturated double-bond, have with the general carbon black commonly used of rubber industry at present or white carbon black with properties-correcting agent, fillers dispersed agent and flow ability modifying agent different from carbon black modified and dissemination.The use of black pigment modifier of the present invention, overcome the black pigment modifier commonly used in the present rubber industry and the deficiency of dispersion agent, solved high sooty NBR sizing material and the multinomial processing characteristics of cross-linked rubber and the contradiction of physical and mechanical properties mutual restriction of reinforcement of filling high consumption.
In the above basic recipe, change the kind and the consumption of dispersion agent and properties-correcting agent, with black pigment modifier of the present invention and present rubber industry general carbon black or white carbon black properties-correcting agent commonly used, the fillers dispersed agent is compared with flow ability modifying agent, use black pigment modifier of the present invention as black pigment modifier and dispersion agent, the processing characteristics of the high sooty NBR sizing material of high filler reinforcement is improved, vulcanization rate to sizing material has no adverse effects, cross-linked rubber has higher draw tensile strength, tensile yield, hardness, thermotolerance, winter hardiness and oil-proofness, the advantage that compression set is little, the over-all properties of cross-linked rubber obviously improves.
Black pigment modifier of the present invention contains specific molecular weight and distribution and multiple functional group, have with present rubber industry general carbon black commonly used or white carbon black with properties-correcting agent, fillers dispersed agent and flow ability modifying agent different from carbon black modified and dissemination, the processing characteristics of the high sooty NBR sizing material of high filler reinforcement is improved, and the over-all properties of cross-linked rubber obviously improves.Mainly show the following aspects:
(1) black pigment modifier of the present invention has similar to Si69 to the sooty modifying function.The oxy radical of carbon blacksurface forms certain chemistry with properties-correcting agent and is connected, and makes and has generated " flexible cross-link bond " between NBR molecular chain and the carbon black.Compare with " rigid " Chemical bond key of carbon black and NBR, so flexible cross-link bond has increased that the interface combines between NBR and the carbon black, be more conducive to the NBR molecular chain in the carbon blacksurface slippage, make the suffered stress of NBR molecule more even, thereby improved elasticity, tensile strength and the tensile yield of carbon black filled cross-linked rubber.Compare with Si69, above-mentioned black pigment modifier does not contain combined sulfur, molecular polarity is bigger, sizing material does not have the danger of incipient scorch in mixing process, the easier and carbon blacksurface group generation chemical reaction of the polar group in the molecule, and can form hydrogen bond with the NBR molecule, strengthened the interaction of carbon black and NBR molecular chain, but coupled action is littler than Si69, and " flexible cross-link bond " is longer, helps improving the winter hardiness of cross-linked rubber.
(2) black pigment modifier of the present invention has the lubricated and dissemination similar with flow ability modifying agent to general dispersion agent.This properties-correcting agent has specific molecular chain and distribution thereof, adsorbed by carbon black easily, may enter in the active site of carbon blacksurface space, form physical adsorption by physical diffusion, carbon black is easier to be disperseed in NBR thereby make, and has improved NBR molecular chain and sooty interface interaction.
(3) black pigment modifier of the present invention has with rubber molecular chain and carbon black interaction force moderate, reduced sooty activity in the cross-linked rubber, slowed down in NBR cross-linked rubber heat-proof aging process, carbon black continues with rubber molecular chain generation chemically crosslinked and aging hardened trend, reduce the compression set of cross-linked rubber, improved the thermotolerance of cross-linked rubber.
(4) compare with Si69, black pigment modifier of the present invention and rubber molecular chain or sooty chemical reactivity are less; Compare with general fatty acid ester dispersion agent, its reactive behavior, Intermolecular Forces and physisorption power are bigger, and less to the lubrication of NBR molecular chain.Therefore, cross-linked rubber reduces at the chemical reaction between the rubber molecular chain, between rubber molecular chain and the carbon black, between the carbon black particle in high temperature compressed process, and the degree of rubber molecular chain slippage reduces, thereby improves the compression set performance of cross-linked rubber.
(5) compare with general fatty acid ester dispersion agent, the volatility of black pigment modifier of the present invention is little, is not easy thermolysis, thereby has increased the thermotolerance of cross-linked rubber.
Embodiment
(1) the physical mechanical chemical property of the mooney viscosity of sizing material and vulcanization characteristics and cross-linked rubber
The kind of several properties-correcting agent and dispersion agent and consumption influence shown in table 2 and the table 3 the physical mechanical chemical property of the high mooney viscosity of filling the NBR sizing material of HAF and vulcanization characteristics and cross-linked rubber.
As can be seen from Table 2, the dispersion agent and the properties-correcting agent that add same amount, the mooney viscosity of sizing material and minimal torque have decline in various degree, the tensile strength of cross-linked rubber, tensile yield, tear strength, shock elasticity, heat-resisting air aging, oil-proofness, compression tension set and winter hardiness have raising in various degree.These several properties-correcting agent or dispersion agent are described to the modification of HAF be dispersed with in various degree help, thereby have improved the flowability of sizing material and the comprehensive physics mechanochemistry performance of cross-linked rubber.But the adding of dispersion agent Dispergator FL, Aflux 42, WB 212, Aktiplast T60, make time of scorch, the sulfurizing time of sizing material that in various degree prolongation be arranged, vulcanization rate descends, and illustrates that these several dispersion agents have certain influence to the sulfuration of sizing material.
Table 2: several properties-correcting agent and dispersion agent are to the high NBR Effect on Performance of filling of HAF
| Specimen coding | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| Dispersion agent or properties-correcting agent kind | Blank | Disper- gator FL | Aflux 42 | WB212 | Aktip- last T60 | Si69 | Black pigment modifier of the present invention |
| Mooney viscosity ML 1+4，100℃ | 70.1 | 63.6 | 65.8 | 64.5 | 64.4 | 67.2 | 66.3 |
| The vulcanization characteristics of sizing material (170 ℃) | |||||||
| Time of scorch t 10/min | 0.53 | 0.65 | 0.56 | 0.72 | 0.76 | 0.48 | 0.57 |
| Sulfurizing time t 90/min | 1.46 | 1.49 | 1.55 | 1.62 | 1.75 | 1.39 | 1.51 |
| Vulcanization rate Vc/min -7 | 56.5 | 53.3 | 49.8 | 47.5 | 46.1 | 58.3 | 52.6 |
| Minimum torque M L/(dNm) | 27.75 | 23.10 | 22.82 | 21.61 | 22.97 | 24.85 | 23.87 |
| Torque capacity M H/(dNm) | 52.76 | 49.33 | 48.74 | 49.79 | 48.65 | 54.37 | 52.41 |
| Cross-linked rubber normality performance | |||||||
| Hardness (Shore A) | 78 | 76 | 75 | 76 | 74 | 77 | 76 |
| 100% stress at definite elongation/MPa | 4.56 | 4.83 | 4.69 | 4.86 | 4.58 | 4.97 | 4.76 |
| Tensile strength/MPa | 18.5 | 20.6 | 21.7 | 22.3 | 21.1 | 24.2 | 23.3 |
| Tensile yield/% | 290 | 355 | 360 | 390 | 380 | 350 | 370 |
| Setafter break/% | 12 | 10 | 14 | 14 | 12 | 6 | 6 |
| Tear strength/(KN/m) | 39.6 | 52.5 | 49.3 | 47.2 | 45.8 | 43.5 | 48.2 |
| Shock elasticity/% | 35 | 39 | 40 | 42 | 43 | 42 | 43 |
| Thermal aging property | |||||||
| Changes in hardness/degree | +12 | +9 | +10 | +11 | +10 | +8 | +6 |
| Tensile strength velocity of variation/% | +56.3 | +48.8 | +40.5 | +46.1 | +42.0 | +36.7 | +28.1 |
| Tensile yield velocity of variation/% | -28.6 | -25.4 | -23.8 | -31.6 | -23.5 | -19.2 | -15.7 |
| Oil-proofness | |||||||
| Changes in hardness (Shore A) | +1 | +2 | +2 | +3 | +3 | +1 | +2 |
| Tensile strength velocity of variation/% | +28.3 | +21.4 | +24.7 | +18.6 | +22.7 | +20.1 | +18.0 |
| Tensile yield velocity of variation/% | -31.4 | -25.8 | -27.3 | -29.6 | -28.3 | -16.6 | -15.9 |
| Volume change/% | +4.5 | +6.3 | +5.7 | +5.3 | +6.9 | +2.4 | +2.7 |
| Compression set/% | 25.2 | 24.6 | 26.8 | 23.1 | 22.5 | 17.3 | 13.1 |
| Temperature limit of brittleness/℃ | -27 | -33 | -35 | -36 | -34 | -28 | -37 |
Annotate: (1) basic recipe (mass parts): NBR (Perbunan NT3445), 100; Zinc oxide, 6.0; Stearic acid, 1.2; Anti-aging agent TMDQ (2,2,4-trimethylammonium-1,2-dihydroxyl caye quinoline polymkeric substance), 1.5; Antioxidant MB I (2-mercaptobenzimidazole), 1.5; Promotor TB
zTD (tetra-benzyl thiram disulfide), 2.0; Accelerator CBS (N cyclohexyl 2 benzothiazole sulfenamide), 1.5; Sulfur, 0.5; High wear-resistant carbon black (H/AF, N330), 50; Plasticizer DOP (dioctyl phthalate (DOP)), 5.0; Dispersion agent and properties-correcting agent (change kind), 2.0.(2) sample cure conditions: 170 ℃ * 4.0min.
It can also be seen that from table 2, compare with black pigment modifier of the present invention with Si69, add the mooney viscosity of sizing material of several dispersion agents and minimal torque descend more obvious, the heat-resisting air aging of its cross-linked rubber, heat resistant oils, compression set poor-performing.Though this is because the adding of these several dispersion agents helps the dispersion of carbon black in rubber, the processing characteristics of improving sizing material is more obvious, but because its intermolecular interaction is less, can obviously influence between the rubber molecule after the adding, the interaction between rubber molecule and the carbon black, and it is stable inadequately under heat and stress, carbon black is not had modifying function, thereby make the easier relative slippage of rubber molecule.
Example in the comparison sheet 2 in example 6# and example 7# and the table 3 can be found, compare with black pigment modifier of the present invention, under the same amount situation, owing to contain combined sulfur in the Si69 molecule, can participate in the vulcanization reaction of rubber, the adding of Si69 reduces the time of scorch of sizing material and sulfurizing time, and the thermotolerance of cross-linked rubber, compression set performance and winter hardiness are poor slightly, the Si69 consumption is big more, and this trend is obvious more; And along with the increase of Si69 consumption, the stress at definite elongation of cross-linked rubber increases, and tear strength is on a declining curve.
This is because Si69 participates in the vulcanization reaction of rubber, makes due to the cross-linking density of cross-linked rubber increases.
Example in the contrast table 2 and the example in the table 3 find that the processing characteristics of the NBR sizing material of the black pigment modifier of the present invention of adding 2.0-6.0 mass parts and the over-all properties of cross-linked rubber are best, and the sulfuration of sizing material is had no adverse effects.This illustrates that black pigment modifier of the present invention is more more obvious than Si69 and dispersion agent Dispergator FL, Aflux 42, WB212, Aktiplast T60 to sooty modification and dispersion effect.
Table 3: black pigment modifier of the present invention and Si69 consumption are to the high NBR Effect on Performance of filling of HAF
| Specimen coding | 8# | 9# | 10# | 11# | 12# | 13# | 14# | 15# |
| Si69 consumption (mass parts) | 1.0 | 4.0 | 6.0 | / | / | / | / | / |
| Black pigment modifier consumption of the present invention (mass parts) | / | / | 0.5 | 1.0 | 4.0 | 6.0 | 7.0 | |
| Mooney viscosity ML 1+4，100℃ | 69.7 | 66.6 | 63.8 | 69.3 | 68.1 | 64.7 | 62.8 | 61.5 |
| The vulcanization characteristics of sizing material (170 ℃) | ||||||||
| Time of scorch t 10/min | 0.55 | 0.40 | 0.37 | 0.55 | 0.53 | 0.54 | 0.55 | 0.52 |
| Sulfurizing time t 90/min | 1.41 | 1.27 | 1.14 | 1.46 | 1.49 | 1.54 | 1.55 | 1.54 |
| Vulcanization rate Vc/min -1 | 56.3 | 60.2 | 63.3 | 56.1 | 55.8 | 52.3 | 51.9 | 53.1 |
| Minimum torque M L/(dNm) | 27.43 | 23.92 | 22.15 | 25.5 | 24.77 | 22.54 | 20.69 | 20.37 |
| Torque capacity M H/(dNm) | 53.61 | 55.46 | 54.72 | 52.8 | 52.54 | 52.63 | 51.78 | 50.33 |
| Cross-linked rubber normality performance | ||||||||
| Hardness (ShoreA) | 75 | 77 | 78 | 76 | 75 | 77 | 76 | 76 |
| 100% stress at definite elongation/MPa | 4.92 | 5.37 | 6.36 | 4.98 | 4.84 | 4.82 | 5.03 | 5.12 |
| Tensile strength/MPa | 22.9 | 24.0 | 22.5 | 19.6 | 24.4 | 23.7 | 21.9 | 22.3 |
| Tensile yield/% | 360 | 320 | 310 | 335 | 390 | 380 | 395 | 410 |
| Setafter break/% | 10 | 6 | 5 | 12 | 9 | 7 | 7 | 8 |
| Tear strength/(KN/m) | 40.9 | 41.1 | 38.3 | 40.2 | 44.5 | 55.5 | 58.7 | 58.3 |
| Shock elasticity/% | 38 | 43 | 42 | 36 | 39 | 44 | 45 | 45 |
| Thermal aging property | ||||||||
| Changes in hardness (Shore A) | +9 | +10 | +10 | +10 | +9 | +7 | +6 | +8 |
| Tensile strength velocity of variation/% | +42.1 | +32.5 | +34.9 | +38.4 | +36.3 | +27.8 | +28.4 | +29.2 |
| Tensile yield velocity of variation/% | -24.5 | -17.9 | -22.6 | -26.9 | -22.1 | -14.7 | -16.6 | -17.5 |
| Oil-proofness | ||||||||
| Changes in hardness (Shore A) | 0 | +2 | +1 | +2 | +2 | +1 | 0 | +1 |
| Tensile strength velocity of variation/% | +26.1 | +18.1 | +23.1 | +27.4 | +25.4 | +16.9 | +19.3 | +18.7 |
| Tensile yield velocity of variation/% | -23.5 | -17.4 | -19.2 | -29.8 | -22.8 | -17.1 | -18.7 | -16.5 |
| Volume change/% | +3.5 | +1.9 | +1.0 | +4.0 | +3.1 | +3.9 | +3.7 | +3.3 |
| Compression set/% | 19.9 | 16.4 | 18.6 | 22.6 | 17.5 | 13.9 | 16.4 | 18.7 |
| Temperature limit of brittleness/℃ | -27 | -29 | -27 | -29 | -30 | -38 | -38 | -37 |
Annotate: basic recipe is identical with table 2.
Example 7# in the contrast table 2 and example 11#, 12# in the table 3,13#, 14#, 15# find, at black pigment modifier consumption of the present invention during less than 1.0 mass parts, not obvious to sooty modification and dispersion effect, consumption is during greater than 6.0 parts, and the heat-resistant air aging property of cross-linked rubber and compression set performance have the trend of reduction.
(2) RPA that adds the NBR sizing material of Si69 and black pigment modifier of the present invention analyzes
Under low strain, the Young's modulus and the viscosity of sizing material that adds Si69 and black pigment modifier of the present invention is bigger, and it is a large amount of in conjunction with glue to illustrate that sizing material after the modification has formed; Along with strained increases, the Young's modulus of sizing material and viscosity have reduction in various degree, and it is bigger to add behind the properties-correcting agent Young's modulus and viscosity degradation.
Under the same strain situation, the modular ratio that adds black pigment modifier sizing material of the present invention adds the slightly little of Si69, sizing material formed more in conjunction with glue after this explanation might add Si69, more likely because the coupled action of black pigment modifier of the present invention is littler than Si69, " flexible cross-link bond " is longer, help improving winter hardiness, shock elasticity and the compression tension set performance of cross-linked rubber, and the living thermal phenomenon when mixing when reducing sizing material.
(3) sem analysis of cross-linked rubber
The section of cross-linked rubber that does not add properties-correcting agent is more level and smooth relatively, and there is more bigger carbon black coacervate in section; And the section that adds the cross-linked rubber of Si69 and black pigment modifier of the present invention exists significantly uneven, carbon black particle quantity of reuniting and particle diameter reduce, interface between itself and the rubber matrix is fuzzyyer, this explanation Si69 and black pigment modifier of the present invention help improving the sooty dispersion effect really and improve carbon black and rubber matrix between interaction.
Test method:
Mixing in the mill of XSK-160 type, the order of pressing rubber, carbon black, black pigment modifier, dispersion agent, promoting agent, Sulfur, anti-aging agent and softening agent adds, and adds promotor at last, and thin-pass is also played the triangle bag 6 times, relaxes roll spacing to 3mm, 5 slices of clot.Measure the vulcanization characteristics of sizing material under 170 ℃ with P3555B2 disc type vulkameter then, vulcanize on QLB-D400 * 400 electrothermal plate vulcanizers, cure conditions is 170 ℃ * 10MPa * 4min.
Mooney viscosity is pressed the GB/T1232-1992 test; The vulcanization characteristics of sizing material is used P3555B
2The disc type vulkameter is determined at 170 ℃ of tests down; The tensile stress-strain performance is pressed the GB528-1998 test, and I type sample, draw speed are 500mm/min; Tear strength is pressed the GB/T529-1999 test, perpendicular type sample, draw speed 500mm/min; Hardness (Shore A) is pressed the GB531-1999 test; Shock elasticity is pressed the GB1681-1991 test; Thermal aging property press GB/T3512-1999 test (120 ℃ * 72h); Oil-proofness, the ASTM1# standard oil, by the test GB1690-1998 (120 ℃ * 72h); Compression set, press GB/T7759-1996 measure (120 ℃ * 72h), rate of compression is 25%; Temperature limit of brittleness is pressed the GB/T1682-1992 test; The rubber machining analyzer test, the sizing material of getting about 5g is tested on rubber machining analyzer, and setpoint frequency is 6r/min, and temperature is under 100 ℃, the Young's modulus of sizing material and strained relation curve; The SEM of cross-linked rubber section test will be observed on scanning electronic microscope behind the cross sectional slice of cross-linked rubber tension specimen, the metal spraying.
Claims (7)
1. a nitrile rubber sizing material that uses black pigment modifier is characterized in that described nitrile rubber sizing material is mixed by mass fraction by following material: NBR dosage 100 mass parts; Zinc oxide dosage 0.1～20 mass parts; Stearic acid dosage 0.1～20 mass parts; Aging inhibitor dosage 0.1～20 mass parts; Accelerator level 0.1～20 mass parts; Sulphur dosage 0.1～20 mass parts; Carbon black loading 0.1～150 mass parts; Plasticizer consumption 0.1～150 mass parts; Black pigment modifier consumption 0.1～7.0 mass parts.
2. the nitrile rubber sizing material of use black pigment modifier according to claim 1 is characterized in that described nitrile rubber sizing material is mixed by mass fraction by following material: NBR dosage 100 mass parts; Zinc oxide dosage 6.0 mass parts; Stearic acid dosage 1.2 mass parts; Anti-aging agent TMDQ consumption 1.5 mass parts; Antioxidant MB I consumption 1.5 mass parts; Promotor TB
zTD consumption 2.0 mass parts; Accelerator CBS consumption 1.5 mass parts; Sulphur dosage 0.5 mass parts; High wear-resistant carbon black consumption 50 mass parts; Plasticizer DOP consumption 5.0 mass parts; Black pigment modifier consumption 2.0～6.0 mass parts.
3. the nitrile rubber sizing material of use black pigment modifier according to claim 1 and 2 is characterized in that: above-mentioned black pigment modifier is the compound of functional groups such as fluorine-containing, ehter bond and unsaturated double-bond.
4. the nitrile rubber sizing material of use black pigment modifier according to claim 1 and 2 is characterized in that: above-mentioned anti-aging agent is that TMDQ is 2,2, and 4-trimethylammonium-1,2-dihydroxyl quinoline polymkeric substance and MBI are also using of 2-mercaptobenzimidazole.
5. the nitrile rubber sizing material of use black pigment modifier according to claim 1 and 2 is characterized in that: above-mentioned promotor is TB
zTD is that tetra-benzyl thiram disulfide and CBS are also using of N cyclohexyl 2 benzothiazole sulfenamide.
6. the nitrile rubber sizing material of use black pigment modifier according to claim 1 and 2 is characterized in that: above-mentioned softening agent is that DOP is a dioctyl phthalate (DOP).
7. the nitrile rubber sizing material of use black pigment modifier according to claim 1 is characterized in that: above-mentioned carbon black is a high wear-resistant carbon black.
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